Evaluation of the electrochemical behavior of carbon paste
electrode (CPE) with chalcopyrite (CuFeS2) in the
presence of ferrous ions Delfino, F.A.A.; Bevilaqua, D.; Fujivara, C. S.; Benedetti, A. V. Universidade Estadual Paulista Rua Prof.Francisco Degni, 55 Araraquara SP - Brasil denise@iq.unesp.br The chalcopyrite mineral sulfide (CuFeS2) is one of the sources for obtaining copper, particularly by pyrometallurgical processes. The requirement of using a corrosive process with high cost is due to slow kinetic of chalcopyrite dissolution. However, the biohydrometallurgy, economically and environmentally favorable process, has been developed as an alternative. This process uses microorganisms, especially the acidophilic bacteria Acidithiobacillus ferroxidans, which are capable of promoting the oxidation of minerals sulfides and the recovery of copper. In the specific case of CuFeS2, bacteria oxidize Fe2+ to Fe3+ ions, which attack the mineral sulfide. However, the presence of Fe3+ ions increases the redox potential and can cause the precipitation of non-stoichiometric sulfides, sulfur and jarosite hindering the removal of copper. In this context, the control of the redox potential through the couple Fe 3+/ Fe2+ can be an alternative for process improvement. In this work we present an electrochemical study using carbon paste electrode (CPE) with CuFeS2 in different concentrations of Fe2+ ions in order to evaluate the possible interaction between these ions and mineral sulfide in the absence of bacteria. Measurements of Electrochemical Impedance Spectroscopy (EIS) were performed for 97 h using CPE-graphite and CPE-CuFeS2 in T&K medium without the addition of Fe2+. Sequentially, the CPE-CuFeS2 was analyzed using T&K medium with [Fe2+] = 0.1, 0.2 or 0.3 mol L-1. The CPE-graphite showed a capacitive behavior with high modulus impedance value. The Bode plots showed one time constant in the region of low frequency possibly related to the graphite response. In the case of CPE-CuFeS2 in T&K medium one time constant in the region of low frequencies was observed which was attributed to the chalcopyrite response. This time constant showed a phase angle around -60o and tends to increase with the immersion time. This time constant is probably related to the oxidation of the mineral surface (elemental sulfur formation, and iron and/or copper dissolution) in acidic medium (pH 1.8), which decreases the surface electroactivity. As cathodic reaction probably both the H+ and O2 may be reduced. For the solution of Fe2+ 0.1 mol L-1 no significant changes in the EIS spectra was observed. For the solutions with 0.2 and 0.3 mol L -1 of Fe2+ a single time constant was observed during the test which may be related to iron oxidation. The diffusion characteristic observed in the EIS spectra of chalcopyrite diminished in 0.2 mol L-1 Fe2+, and almost disappeared in 0.3 mol/L Fe2+. It is possible that the main process in the presence of iron(II) ions is their oxidation. On the other hand, it is possible that Fe2+ reacts with CuFeS2 and cause partial dissolution of the mineral sulfide, making it still more refractory. More electrochemical and microscopy studies are in progress to elucidate the interaction between chalcopyrite and ferrous ions.